Optically brightened textile materials



United States Patent Office 3,082,114 Patented Mar. 19, 1963 3,082,114 OPTICALLY BRIGHTENED TEXTILE MATERIALS Heinz Balli, Coelbe, near Marburg (Lahn), and Dieter Leuchs, Manfred Hehl, Wolfgang Grunwald, and swald Schmidt, Ludwigshafen (Rhine), Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Mar. 30, 1960, Ser. No. 18,501 Claims priority, application Germany Apr. 1, 1959 9 Claims. (Cl. 117-335) This invention relates to optically brightened textile materials of polymers of acrylonitrile and cellulose acetate.

It has heretofore been known that textile materials of polymers of acrylonitrile and cellulose acetate can be brightened by the application of optical brightening agents to these materials. The term textile materials is meant to include fibers, flocks, yarns, threads, woven and nonwoven fabrics and films. The term cellulose acetate is intended to include both cellulose Z /t-acetate and cellulose triacetate and also cellulose acetates, the acetyl content of which lies between 2 /2 and 3 groups per glucose moiety. The term polymers of acrylonitrile is meant to include polyacrylonitrile itself and copolymers of acrylonitrile with other polymerizable compounds as, for example, vinyl chloride and vinyl acetate, the acrylonitrile component determining the tinctorial properties of the said copolymers. Such copolymers preferably contain more than 50% of their weight of acrylonitrile. In addition .to cellulose acetate and polymers of acrylonitrile the textile materials to be brightened may contain any of the usual additives as, for example, dyestuffs and textile auxiliaries.

The optical brightening agents are conventionally ap plied to the said materials in an aqueous suspension. The use of aqueous suspensions of optical brightening agents, however, has some disadvantages; thus, for example, the suspensions may flocculate and thus cause an unlevelled brightening eifect.

It is therefore desirable to apply optical brightening agents to the said materials in aqueous solutions. Unfortunately, however, most of the prior optical brightening agents do not go on to said materials from aqueous solutions.

There are known certain monomethine cyanines which can be applied as brightening agents to textile materials consisting of polymers of acrylonitrile or cellulose acetate, in aqueous solution but these monomethine cyanines give a greenish hue to the brightened textile materials rather than a bluish hue which is much more desirable.

It is an object of this invention to provide optically brightened textile materials with an excellent whiteness degree which is particualrly fast to sunlight and wet treatment.

We have found that the object of the invention is achieved by treating textile materials of polymers of acrylonitrile or cellulose acetate with salt-like azamonomethine cyanine compounds of the general formula in which Y and Y are identical or different and represent hydrogen atoms, methyl groups or methoxy groups and X is the equivalent of an anion.

The nature of the anion has no significance for the brightening action of the said azamonomethine cyanines. It may be an inorganic anion, as for example a chloride, bromide, iodide, perchlorate or sulfate anion, or an orcorporating the azamonomethine cyanines to be brightened before or during the shaping of the same. More advantageously, however, the azamonomethine cyanines can be applied to the shaped textile materials themselves from an aqueous solution by the usual dyeing processes.

For the production of a strong brightening effect small amounts are usually sufiicient, as for example 0.01 to 5%,

preferably 0.05 to 0.5%, of azarnonomethine cyanine with reference to the Weight of the material to be brightened.

The white effects obtained with the azamonomethine cyanines on the above mentioned textile materials are moreover fast to alkali metal chlorite solutions which are I As a result the optical brightening of the said materials can be carried out.

used for bleaching these materials.

before bleaching or even simultaneously with an alkali metal chlorite bleach, for example a sodium chlorite bleach. Furthermore, the White effects achieved by the process according to this invention are outstandingly fast 5 to the action of sunlight and to the usual wet treatments, such as washing.

The following examples will further illustrate the inf vention but the invention is not restricted to these examples. The parts given in the examples are parts by Weight.

Example 1 parts of previously washed polyacrylonitrile fabric are treated for 30 minutes at 98 C. in a bath which contains 3,000 parts of Water, 003 to 0.3 part of the azamonomethine cyanine:

3 parts of 30% acetic acid and 0.3 part of sodium acetate. After rinsing and drying, the treated fabric has a pure white appearance. The brightening effect is eminently fast to light and washing.

Example 2 100 parts of a polyacrylonitrile skein yarn are kept moving for 30 minutes at 98 to 100 C. in a bath of 3,000 parts of water, 0.03 to 0.3 part of the azamonomethine cyanine:

ianooso,

2 parts of concentrated sulfuric acid and 10 parts of crystallized sodium sulfate.

As compared with the untreated skein yarn, the treated yarn appears pure white.

The compounds are water- By using the compound of the formula:

OCH3

Example 3 A washed fabric of polyacrylonitrile staple fiber is treated for 60 minutes at a liquor ratio of 1:30 in a bath containing, in 1,000 parts of Water, 2 parts of sodium chlorite, 0.3 part of the sodium salt of oleic acid methyl tauride, 0.5 part of tetrasodium pyrophosphate, 0.3 part of sodium acetate and 0.01 to 0.1 part of the azamonomethine cyanine used in Example 1. The pH value of the bath is adjusted to 3.5 to 4 with formic acid prior to the introduction of the fabric. After rinsing and drying, the treated fabric has a brilliant white appearance.

The same effect is achieved by using the azamonomethine cyanine of the first paragraph of Example 2 instead of the azamonomethine cyanine of Example 1.

Example 4 100 parts of a washed cellulose acetate fabric are treated I CH CH in which Y and Y each represent a member selected from the group consisting of hydrogen, methyl and methoxy, and X is an anion.

2. A textile material as claimed in claim 1 containing about 0.01 to 5.0% by weight thereof of said azamonomethine cyanine.

3. A textile material as claimed in claim 1 containing about 0.1 to 0.5% by Weight thereof of said azamonomethine cyanine.

4 4. A textile material as claimed in claim 2 wherein the azamonomethine cyanine has the formula CH CH3 5. A textile material as claimed in claim 2 wherein the azamonomethine cyanine has the formula s CH: CH:

6. A textile material as claimed in claim 2 wherein the azamonomethine cyanine has the formula s s IHEGO- 00m CH3 CH with an aqueous bath containing a bleaching agent and an azamonomethine cyanine of the formula in which Y and Y each represent a member selected from the group consisting of hydrogen, methyl and methoxy, and X is an anion.

8. A process as claimed in claim 7 wherein said bleaching agent is an alkali metal chlorite.

9. A process as claimed in claim 8 wherein said b1eaching agent is sodium chlorite.

References Cited in the file of this patent UNITED STATES PATENTS UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,082, 114 March 19, 1963 Heinz Balli et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 61 to 68, the right-hand portion of the formula, for "H COSO read H COSO column 3, lines 41 to 4?, central portion of the formula, for "C-N-C" read CN= Signed and sealed this 24th day of December 1963.

(SEAL) Attest:

EDWIN L, REYNOLDS ERNEST W. SWIDER Attesting Officer Ac ting Commissioner of Patents 

1. A TEXTILE MATERIAL SELECTED FROM THE CLASS CONSISTING OF POLYMERS OF ACRYLONITRILE AND CELLULOSE ACETATE WHICH IS OPTICALLY BRIGHTENED WITH AN AZAMONONMETHINE CYANINE OF THE FORMULA 